Deactivatable biocides for hydrocarbonaceous products

Abstract

The present invention relates to the use of deactivatable biocides for hydrocarbonaceous products, in particular, rapidly biodegradable hydrocarbonaceous products. The present invention also relates to methods of inhibiting growth and reproduction of microorganisms in hydrocarbonaceous products, in particular, in rapidly biodegradable hydrocarbonaceous products, containing minor amounts of aqueous liquids. The deactivatable biocides of the present invention may be derived from a Fischer-Tropsch process.

What is claimed is:  
     
       1. A biologically inhibited hydrocarbonaceous product comprising: 
       a) Fischer-Tropsch-derived liquid products subject to biological growth; and  
       b) an effective amount of a deactivatable biocide to resist visible growth of micro-organisms for at least 10 days under ambient conditions when exposed to a certified inoculant,  
       wherein the deactivatable biocide is irreversibly deactivated after the period in which biological growth is expected.  
     
     
       2. A product according to  claim 1 , wherein the Fischer-Tropsch products are selected from the group consisting of Fischer-Tropsch naphtha, Fischer-Tropsch jet fuel, Fischer-Tropsch diesel fuel, Fischer-Tropsch solvent, Fischer-Tropsch lube base stock, Fischer-Tropsch lube base oil, Fischer-Tropsch lube base oil feedstock and mixtures thereof. 
     
     
       3. A product according to  claim 1 , wherein the Fischer-Tropsch products have a branching index of less than five. 
     
     
       4. A product according to  claim 1 , wherein the biocide is selected from the group consisting of aldehydes, alkynes, and mixtures thereof. 
     
     
       5. A product according to  claim 4 , wherein the biocide is selected from the group consisting of glutaraldehyde, 1-hexyne, propargyl alcohol, and mixtures thereof. 
     
     
       6. A product according to  claim 3  wherein the biocide is a Fischer-Tropsch-derived deactivatable biocide. 
     
     
       7. A method of inhibiting growth and reproduction of microorganisms in hydrocarbonaceous products containing minor amounts of water, comprising the steps of: 
       a) providing a hydrocarbonaceous product;  
       b) adding an effective amount of a deactivatable biocide to resist visible growth for at least 10 days under ambient conditions when exposed to a certified inoculant;  
       c) adding an effective amount of neutralizing agent to deactivate the biocide after the period in which growth and reproduction of microorganisms is expected.  
     
     
       8. A method according to  claim 7 , wherein the biocide is added at a concentration of less than 1 wt %. 
     
     
       9. A method according to  claim 7 , wherein the biocide is added at a concentration of less than 1000 ppm. 
     
     
       10. A method according to  claim 9 , wherein the biocide is added at a concentration of less than 100 ppm. 
     
     
       11. A method according to  claim 7 , wherein the biocide is an aldehyde and the neutralizing agent is a nitrogen-containing compound selected from the group consisting of amines, amino acids, amino alcohols, and mixtures thereof. 
     
     
       12. A method according to  claim 7 , wherein the biocide is an alkyne and the neutralizing agent is a hydrogenation catalyst and H 2 . 
     
     
       13. A method according to  claim 11 , wherein the biocide is glutaraldehyde and the nitrogen-containing compound is monoethanolamine. 
     
     
       14. A method of inhibiting growth and reproduction of microorganisms in hydrocarbonaceous products containing minor amounts of aqueous liquids, comprising the steps of: 
       a) providing a rapidly biodegradable hydrocarbonaceous product;  
       b) adding an effective amount of a deactivatable biocide to resist visible growth for at least 10 days under ambient conditions when exposed to a certified inoculant; and  
       c) adding an effective amount of a neutralizing agent to deactivate the biocide after the period in which growth and reproduction of microorganisms is expected.  
     
     
       15. A method according to  claim 14 , wherein the rapidly biodegradable hydrocarbonaceous product is Low Aromatics Diesel Fuel or Fischer Tropsch derived liquid hydrocarbonaceous product. 
     
     
       16. A method according to  claim 14 , further comprising a step d) separating the aqueous liquid from the hydrocarbonaceous product. 
     
     
       17. A method according to  claim 16 , wherein the separation step d) is performed after adding the neutralizing agent. 
     
     
       18. A method according to  claim 16 , wherein the separation step d) is performed after adding the neutralizing agent. 
     
     
       19. A method according to  claim 16 , further comprising a step e) treating the aqueous liquid in a biological oxidation facility to remove hydrocarbons. 
     
     
       20. A method according to  claim 15 , wherein the biocide is an alkyne and the neutralizing agent is a hydrogenation catalyst and H 2 . 
     
     
       21. A method according to  claim 15 , wherein the biocide is glutaraldehyde and the neutralizing agent is monoethanolamine. 
     
     
       22. A method of inhibiting growth and reproduction of microorganisms in Fischer-Tropsch-derived liquid products, containing minor amounts of water, comprising the steps of: 
       a) performing a Fischer-Tropsch synthesis process;  
       b) isolating Fischer-Tropsch-derived liquid products from the Fischer-Tropsch process;  
       c) isolating Fischer-Tropsch-derived deactivatable biocides from the Fischer-Tropsch process;  
       d) mixing the Fischer-Tropsch-derived liquid products with an effective amount of the Fischer-Tropsch-derived biocide to resist visible growth for at least 10 days under ambient conditions when exposed to a certified inoculant; and  
       e) adding an effective amount of neutralizing agent to deactivate the biocide after the period in which biological growth is expected.  
     
     
       23. The method according to  claim 22 , wherein the Fischer-Tropsch derived deactivatable biocides are isolated by distillation or chromatographic separation. 
     
     
       24. The method according to  claim 22 , further comprising a step f) separating the water from the hydrocarbonaceous product. 
     
     
       25. The method according to  claim 24 , further comprising a step g) treating the water in a biological oxidation facility to remove hydrocarbons. 
     
     
       26. A method according to  claim 22 , wherein the biocide is an alkyne and the neutralizing agent is a hydrogenation catalyst and H 2 . 
     
     
       27. A method according to  claim 22 , wherein the biocide is glutaraldehyde and the neutralizing agent is monoethanolamine. 
     
     
       28. A method of inhibiting growth and reproduction of microorganisms in Fischer-Tropsch-derived liquid products containing minor amounts of water, comprising the steps of: 
       a) performing Fischer-Tropsch synthesis on syngas to provide a product stream;  
       b) fractionally distilling the product stream and isolating liquid hydrocarbonaceous products and oxygenates;  
       c) subjecting the oxygenates to oxidation to form aldehydes;  
       d) blending the liquid hydrocarbonaceous products with an effective amount of the aldehydes to resist visible growth for at least 10 days under ambient conditions when exposed to a certified inoculant;  
       e) adding an effective amount of neutralizing agent to deactivate the aldehydes after the period in which biological growth is expected.  
     
     
       29. A method according to  claim 28 , wherein the aldehydes are glutaraldehyde and the neutralizing agent is monoethanolamine. 
     
     
       30. A method according to  claim 28 , wherein the oxygenates are isolated from light Fischer Tropsch products. 
     
     
       31. A method according to  claim 28 , wherein the oxygenates are isolated from waste-water generated as part of the Fischer-Tropsch process. 
     
     
       32. A method of inhibiting growth and reproduction of microorganisms in Fischer-Tropsch-derived liquid products containing minor amounts of water, comprising the steps of: 
       a) performing Fischer-Tropsch synthesis on syngas to provide a product stream;  
       b) fractionally distilling the product stream and isolating liquid hydrocarbonaceous products and olefins;  
       c) subjecting the olefins to dehydrogenation to form alkynes;  
       d) blending the liquid products with an effective amount of the alkynes to resist visible growth for at least 10 days under ambient conditions when exposed to a certified inoculant;  
       e) adding an effective amount of neutralizing agent to deactivate the alkynes after the period in which biological growth is expected.  
     
     
       33. A method according to  claim 32  wherein the alkynes are primary alkynes and the neutralizing agent is a hydrogenation catalyst and H 2 . 
     
     
       34. A method according to  claim 32 , wherein the olefins are formed from a thermal cracking process which uses a heavy Fischer Tropsch feed derived from a Fischer Tropsch process. 
     
     
       35. A method according to  claim 32 , wherein the olefins are isolated from light Fischer Tropsch products.